CN113876951A - Preparation and application of ferric oxide/gold nano-composite with cascade catalysis effect - Google Patents
Preparation and application of ferric oxide/gold nano-composite with cascade catalysis effect Download PDFInfo
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- 230000000694 effects Effects 0.000 title abstract description 12
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 1
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- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 208000021959 Abnormal metabolism Diseases 0.000 description 1
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A61K33/00—Medicinal preparations containing inorganic active ingredients
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- A61K9/00—Medicinal preparations characterised by special physical form
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Abstract
The invention discloses a preparation method of a ferric oxide/gold nano-composite with a cascade catalysis effect and a preparation method thereofApplication, belonging to the technical field of nano biological materials. The invention calcines the hydroxyl ferric oxide with porous structure at high temperature to obtain Fe2O3The gold nanoparticles and the loaded water-soluble polyethylene glycol are dotted to obtain Fe3O4@ Au-PEG multifunctional nanoprobes. In the probe, Fe2O3The gold has peroxidase-like catalytic ability, and the Au has glucose oxidase-like catalytic ability and can catalyze the conversion of glucose into gluconic acid, and the process consumes oxygen and generates hydrogen peroxide. At the same time, Fe2O3Catalyzing the conversion of hydrogen peroxide to oxygen, forming a cascade of catalysis. When the probe is used for treating tumors, the cascade catalysis is realized by starving cancer cells through consuming glucose; iron ions induce cancer cell death by the pathway of iron death; in near-infrared illumination, Au causes cancer cell death by light and heat. Therefore, the probe can effectively treat the cancer through various ways.
Description
Technical Field
The invention belongs to the technical field of nano biological materials, and particularly relates to a ferric oxide/gold nano composite (Fe) with a cascade catalytic effect2O3Au-PEG) nano probe preparation and application.
Background
Cancer cells have abnormal metabolism and tend to proliferate and grow indefinitely. Due to its heterogeneity, cancer treatment is increasingly difficult. Thus, combination therapy is often used for cancer treatment, and the effect of 1+1 > 2 is achieved in combination therapy as compared to monotherapy. Can achieve better treatment effect by designing a multifunctional nano probe and combining multiple ways of treatment.
Disclosure of Invention
In view of the above, the present invention provides a ferric oxide/gold nanocomposite (Fe) with cascade catalysis2O3preparing/Au-PEG) nanoprobe and application thereof, wherein FeOOH prepared by a one-pot method is calcined at high temperature to obtain Fe with a porous structure2O3Modifying the gold nanoparticles to obtain Fe2O3Au, and is used for preparing a multifunctional tumor treatment probe integrating glucose deprivation, iron death and photo-thermal treatment, thereby realizing the technical problem that the current single cancer treatment means is poor.
The purpose of the invention is realized by a ferric oxide/gold nano composite (Fe) with cascade catalysis2O3The preparation method of the/Au-PEG) nano probe is characterized by comprising the following steps:
(1) synthesizing FeOOH by a hydrothermal method;
(2) SiO the FeOOH obtained in the step (1)2To obtain SiO2Encapsulated FeOOH @ SiO2;
(3) For FeOOH @ SiO obtained in the step (2)2High-temperature calcining is carried out to obtain alpha-Fe2O3；
(4) For alpha-Fe obtained in the step (3)2O3Modifying the gold nanoparticles to obtain Fe2O3/Au；
(5) For Fe obtained in the step (4)2O3/Au is modified by polyethylene glycol to obtain Fe2O3/Au-PEG。
The preparation method of the step (1) comprises the following steps: dissolving a certain amount of ferric chloride hexahydrate in water, transferring the solution into a round-bottom flask, and continuously stirring the solution at 80 ℃ under the condition of refluxing condensed water to obtain a hydrolysate FeOOH.
The step (2) comprises the following specific steps: dissolving FeOOH in ethanol, adding CTAB, ammonia water and TEOS under continuous stirring, and stirring for a long time to obtain SiO2Encapsulated FeOOH @ SiO2。
The step (3) comprises the following specific steps: FeOOH @ SiO2Dissolving in ethanol, and dropwise adding ammonia water for a few times; then calcining the reaction solution at high temperature to obtain Fe2O3@SiO2(ii) a Finally, the SiO is etched by adding NaOH2To obtain Fe2O3。
The step (4) comprises the following specific steps: mixing Fe2O3Dissolving in ethanol, adding gold nanoparticles, and continuously stirring to obtain Fe2O3/Au。
The step (5) comprises the following specific steps: mixing Fe2O3Dissolving Au in ethanol, adding polyethylene glycol, and continuously stirring to obtain Fe2O3/Au-PEG。
The ferric oxide/gold nano composite (Fe) with the cascade catalysis effect obtained by the preparation method of the invention2O3/Au) nanoprobe.
The iron sesquioxide/gold nano composite (Fe) of the invention2O3The application of the/Au) nano probe is characterized by being applied to the preparation of the nano probe for treating tumors.
The nano probe for treating the tumor is a nano probe for treating the tumor by three therapies of hunger, iron death and photo-thermal.
The application is characterized in that the iron sesquioxide/gold nano composite (Fe) is added before the application2O3and/Au) nano probe is modified by polyethylene glycol.
Specifically, to achieve the above objects, according to one aspect of the present invention, there is provided a ferric oxide/gold nanocomposite (Fe) having a cascade catalytic effect2O3The preparation method of the Au-PEG) nano material comprises the following steps:
(1) synthesizing a hydrolysate FeOOH of the iron by a one-pot method;
(2) modifying the SiO with FeOOH obtained in the step (1)2Then calcining to obtain Fe2O3@SiO2And (3) nano materials.
(3) For Fe obtained in the step (2)2O3@SiO2Etching to obtain Fe2O3。
(4) For Fe obtained in the step (3)2O3Modifying the gold nanoparticles to obtain Fe2O3/Au。
Preferably, step (1) is specifically: 0.35 g FeCl3•6H2O was dissolved in 75 mL of water and transferred to a round bottom flask, and the temperature was raised to 80 ℃ under reflux of condensed water, with continuous stirring, to give FeOOH.
Preferably, the stirring time is between 12 h and 20 h.
Preferably, the step (2) is specifically: 40 mg of FeOOH was dissolved in 8 mL of ultrapure water and then transferred to an 80 mL round-bottom flask. Subsequently, 2.4 mL of ammonia water, 0.48 g of CTAB and 160. mu.L of TEOS were added dropwise in small portions. After continuously stirring for 20 h, FeOOH @ SiO is obtained2. Finally, 100 mg of FeOOH @ SiO2Placing the mixture in a muffle furnace, and dropwise adding 480 mg of NH4NO3Then continuously stirring for 6 h at 45 ℃, and then carrying out high-temperature calcination to obtain Fe2O3@SiO2。
Preferably, the calcination is carried out in the range of 500-800 ℃ for 3-5 h.
Preferably, the step (3) is specifically: mixing Fe2O3@SiO2Reacted with 40 mL of 4mol/L NaOH solution at 80 ℃ for 3 h to remove SiO2To obtain Fe2O3。
Preferably, the step (4) is specifically: mixing 9 mg of Fe2O3Dissolving in ethanol solution, adding gold nanoparticles, stirring at room temperature for 3 h to obtain Fe2O3/Au。
According to another aspect of the invention, the application of the ferric oxide nano material is provided, which is used for preparing a nano probe for treating tumors.
Preferably, the nanoprobes for treating tumors are glucose deprivation, iron death, and photothermal; a nano probe for combined treatment of tumors.
Preferably, the ferric oxide/gold nano-composite is modified by polyethylene glycol before application.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the invention synthesizes the hydrolysate of iron through SiO on the surface2After modification, high-temperature calcination is carried out, and SiO is removed by etching with an alkali solution2To obtain porous Fe2O3. Compared with Fe synthesized by the conventional method2O3Fe synthesized by the present invention2O3Has good peroxidase catalytic performance and complete morphology.
(2) According to the invention, the nano-composite of ferric oxide and gold is modified with water-soluble polyethylene glycol, so that the material has better water solubility and biocompatibility.
(3) The invention preferably takes advantage of the porosity of FeOOH as a precursor. In addition, the introduction of iron ions provides a necessary condition for subsequent iron death.
(4) Fe according to the invention2O3The gold nanoparticles have peroxidase catalytic activity, and the gold nanoparticles have glucose oxidase activity, can generate cascade catalytic action when the nano-composite of the two is used as a carrier for cancer treatment, continuously consume glucose around a tumor, and perform starvation treatment on cancer cells in a mode of depriving cancer glucose; meanwhile, the iron ions can further kill tumor cells through an iron death way; in addition, gold nanoparticles can generate a large amount of heat when exposed to light, further killing tumor cells by photothermal therapy. Therefore, the nano probe taking the nano composite as the carrier can realize the tumor treatment in multiple ways simultaneously so as to achieve more effective treatment effect.
(5) Fe synthesized by the invention2O3The Au nanoprobe can be well applied to a mouse xenograft model, and well inhibits the growth of mouse tumors through glucose deprivation/iron death/photothermal combined treatment.
Drawings
FIG. 1 is a graph of synthetic FeOOH and Fe2O3Transmission electron microscopy comparison of/Au with 50 nm and 20 nm scales.
FIG. 2 is Fe2O3Characterization of the ability of Au-PEG to characterize peroxidase using TMB.
FIG. 3 is a graph showing the measurement of Fe2O3The enzyme activity of the glucose oxidase of the Au-PEG solution is used for representing the capability of the probe with the glucose oxidase.
FIG. 4 is Fe2O3After incubation of Au-PEG with cells, the intracellular iron death profile was determined.
FIG. 5 is Fe2O3The change situation of the system temperature of the Au-PEG probe under the illumination of 808 nm is shown.
FIG. 6 is Fe2O3Graph of tumor growth inhibition in tumor model using Au-PEG for mouse xenograft.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a ferric oxide/gold nano composite (Fe) with cascade catalysis effect2O3The preparation method of the Au-PEG) nanoprobe comprises the following steps:
(1) synthesizing a hydrolysate FeOOH of the iron by a one-pot method;
(2) SiO the hydrolysate FeOOH of the iron obtained in the step (1)2Modified to obtain FeOOH @ SiO2High-temperature calcining is carried out to obtain Fe2O3@SiO2。
(3) For Fe obtained in the step (2)2O3@SiO2Etching to remove SiO2To obtain Fe2O3。
(4) For Fe obtained in the step (3)2O3Modifying the gold nanoparticles to obtain Fe2O3/Au。
In some embodiments, step (1) is specifically: 0.35 g of ferric chloride hexahydrate was dissolved in 75 mL of water and transferred to a round bottom flask with a reflux condenser system and stirred continuously at 80 ℃ for 19 h to give FeOOH.
The one-pot method is to stir the aqueous solution of ferric chloride hexahydrate to obtain FeOOH. In some embodiments, the dosage range and reaction time of the salt solution can be adjusted as needed to obtain FeOOH with a suitable morphology. The dosage of the salt solution is as follows: 0.2-0.5 g of the catalyst is dissolved in 75 mL of water, and the reaction time is 12-20 h.
In some embodiments, step (2) is specifically: 0.48 g CTAB was dissolved in 80 mL of ethanol solution, thenAnd then transferred to a round bottom flask. Then 40 mg of FeOOH was weighed out and dissolved in 8 mL of water and added to the round-bottom flask. Then, 2.4 mL of ammonia water and 160 mu L of TEOS are added dropwise under the condition of continuous stirring, and the mixture is continuously stirred for 20 hours to obtain FeOOH @ SiO2. Obtaining Fe by high-temperature calcination2O3@SiO2. In some embodiments, the high temperature calcination is performed at 500-800 deg.C for 3-5 h.
In some embodiments, step (3) is specifically: mixing Fe2O3@SiO2Dissolving in NaOH solution, and continuously stirring at 80 deg.C to remove SiO2To obtain Fe2O3. In some embodiments, the concentration of NaOH is 4mol/L and the etching time is 3-5 h.
The invention also provides the ferric oxide/gold nano composite obtained by the preparation method.
The hydrolysis product FeOOH of the iron prepared in the step (1) of the preparation method is in a porous fusiform shape, the longest side length of the hydrolysis product FeOOH is 200-250 nm, and the hydrolysis product Fe is obtained after high-temperature calcination2O3The morphology remained unchanged, but the porosity was significantly greater.
The ferric oxide/gold nanoprobe prepared by the invention has the catalytic activity of peroxidase and glucose oxidase, and can continuously consume glucose through cascade catalysis. Preferably, the probe is applied to cell therapy or biotherapy, which is capable of consuming glucose around cancer cells to starve the cancer cells by depriving the cancer cells of metabolic materials.
The ferric oxide/gold nanoprobe prepared by the invention also has the capability of iron death, and preferably, when the probe is applied to cell therapy or living body therapy, cancer cells can be treated through the way of iron death.
The ferric oxide/gold nanoprobe prepared by the invention also has the capacity of photothermal conversion, and preferably, when the probe is applied to cell therapy or living body therapy, cancer cells can be killed and killed through photothermal therapy.
The application of the ferric oxide/gold nanoprobe can be used for preparing nanoprobes for treating tumors.
In some embodiments, the tumor-treating nanoprobe is a glucose deprivation/iron death/photothermal combination tumor-treating nanoprobe.
In some embodiments, the iron trioxide/gold nanomaterials are polyethylene glycol modified prior to use to improve their water solubility and biocompatibility as nanoprobes.
The invention also provides the application of the material in a mouse tumor model of xenotransplantation.
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
A preparation method of ferric oxide/gold nano composite comprises the following steps:
(1) taking hydrolysis product FeOOH of ferric chloride hexahydrate as precursor, and calcining at high temperature to obtain Fe2O3。
(2) Fe in (1)2O3Mixing with gold nanoparticles to obtain Fe2O3/Au。
(3) Fe in (2)2O3Reaction of Au with polyethylene glycol to obtain Fe2O3/Au-PEG。
Specifically, in step (1), Fe was prepared by the following method2O3：
0.35 g of ferric chloride hexahydrate was completely dissolved in 75 mL of water, transferred to a round bottom flask with a reflux condenser, stirred continuously at 80 ℃ for 19 h, and centrifuged to give FeOOH. Then, 40 mg FeOOH was added to 80 mL of an anhydrous ethanol solution containing 0.48 g of CTAB, after 30 min of ultrasonication, 2.4 mL of ammonia water was added, 160. mu.L of TEOS was added, after stirring for 10 h, CTAB was removed, and after drying, high-temperature calcination was carried out to obtain Fe2O3@SiO2Then 100 mg of Fe2O3@SiO2Dissolving in 40 mL of 4mol/L sodium hydroxide solution, and stirring at 80 ℃ for 3 h to obtain Fe2O3。
In the step (2), Fe was obtained by the following method2O3/Au:
9 mg of Fe2O3Dissolving in 2 mL of absolute ethanol, adding 2.5 mL of gold complex (the gold complex is a known product and is reported in published documents, the specific synthetic steps are detailed in chem. Mater. 2013, 25, 1761-1768), and continuously stirring for 3 h at room temperature to obtain Fe2O3/Au。
In the step (3), Fe was obtained by the following method2O3/Au-PEG：
10 mg of PEG was dissolved in 2 mL of water and added to 20 mL of a solution containing 10 mg of Fe2O3In Au solution, and then continuously stirring for 24 h to obtain Fe2O3Au-PEG. The effect of the modified PEG here is mainly to give the synthesized MOF better water solubility and biocompatibility.
Example 2
The embodiment provides a synthesis method of an iron sesquioxide/gold nano composite, wherein the material is in a porous structure of a shuttle shape, and the side length of the longest side of the material is 200 nm-250 nm; the gold nanoparticles are uniformly interspersed on the ferric oxide.
The material is prepared by the following preparation method:
(1) preparation of FeOOH
0.35 g of ferric chloride hexahydrate is weighed and dissolved in 75 mL of water, then the solution is transferred to a round-bottom flask with a condensation reflux system, the stirring is continued for 19 hours at the temperature of 80 ℃, the color is changed from colorless to yellow brown, and the precipitate which is yellow brown and is FeOOH is obtained by centrifuging at 8000 rpm for 10 min to remove unreacted metal ions.
As shown in FIG. 1, the obtained FeOOH has a loose and porous structure, a longest side length of 200 nm, and good dispersibility.
（2）FeOOH@SiO2The preparation of (1):
40 mg of FeOOH obtained in step (1) was dissolved in 8 mL of water, and then added to 80 mL of an anhydrous ethanol solution in which 0.48 g of CTAB was dissolved. Then adding 2.4 mL of ammonia water with the mass percentage of 25-28% and 160 mu L of TEOS under continuous stirring, and continuously stirring for 20 h to obtain FeOOH @ SiO2。
（3）Fe2O3The preparation of (1):
FeOOH @ SiO obtained in the step (2)2100 mg was weighed into 80 mL of anhydrous ethanol solution, then 480 mg of ammonium nitrate powder was added slowly with constant stirring, and the reaction was then warmed to 45 ℃ for 6 h. Then, the temperature is raised to 700 ℃ to react for 3 h to obtain Fe2O3@SiO2. Finally, 100 mg of Fe2O3@SiO2Reacting with 40 mL of sodium hydroxide with the concentration of 4mol/L at 80 ℃ for 3 h to remove SiO2To obtain Fe2O3。
（4）Fe2O3Preparation of Au:
firstly, synthesizing gold nanoparticles: 24 mg of chloroauric acid was dissolved in 5 mL of methanol solution, 20 mg of MPA was dissolved in 2 mL of anhydrous methanol solution, and both solutions were stirred at room temperature for 3 hours, centrifuged several times, and resuspended in 8 mL of anhydrous methanol solution to obtain Au-MPA. Next, 9 mg of Fe was weighed2O3Dissolving in 2 mL of anhydrous methanol solution, dropwise adding 2.5 mL of Au-MPA, and continuously stirring at room temperature for 3 h to obtain Fe2O3/Au。
As shown in FIG. 1, is the Fe obtained2O3The shape and appearance of Au transmission electron microscope are shown, and Fe is obtained2O3Au has better dispersibility, and gold nanoparticles are uniformly dispersed in Fe2O3Is shown.
Example 3
Characterization of the cascade catalysis of ferric oxide/gold nano composite and characterization of iron death and photo-thermal performance of the nano composite, comprising the following steps:
in characterizing the cascade catalytic properties of the prepared nanocomposites, the iron trioxide/gold nanocomposites (Fe) synthesized in example 1 or example 22O3/Au) is modified by polyethylene glycol to obtain Fe2O3Au-PEG (specifically prepared by dissolving 10 mg of PEG in 2 mL of water and adding to 20 mL of solution containing 10 mg of Fe2O3In Au solution, and then continuously stirring for 24 h to obtain Fe2O3/Au-PEG），Fe2O3Au-PEG is dissolved in water, reacts with hydrogen peroxide and TMB, and the amount of oxTMB generated in the reaction system is detected within 5 min to characterize Fe2O3The peroxidase catalytic ability of (a). Meanwhile, the enzyme activity of the glucose oxidase of the probe is tested.
FIG. 2 is Fe2O3The ability of Au-PEG peroxidase, FIG. 3 shows Fe2O3the/Au-PEG has the capability of being similar to glucose oxidase, so that the composite probe can perform cascade catalysis and continuously consume glucose.
Characterisation of the produced Fe2O3When treating tumor or cancer cells with iron death pathways, the Au-PEG is co-cultured with the cells and then is subjected to fluorescence detection by using lipopluxo.
FIG. 4 shows that the probe can kill cancer cells by iron death after incubation with the cells.
When the photothermal performance of the probe is characterized, Fe with the concentration of 50 mu g/mL2O3and/Au-PEG is placed under 808 nm laser for illumination, and the temperature rise condition of the system is observed.
FIG. 5 is a graph showing the change in temperature of the probe under light. The results showed that the probe was at 1W/cm2Obvious temperature rise can be seen after the probe is irradiated for 5 min under 808 nm laser, which shows that the probe has good photothermal conversion performance and great potential for photothermal treatment of tumors.
Example 4
The ferric oxide/gold nano composite probe is used for hunger/iron death/photothermal combined treatment to inhibit tumor growth, and comprises the following steps:
(1) preparation of Balb/c mice subcutaneous tumor model: mouse breast cancer cells 4T1 at 37 deg.C with 5% CO2Culturing in DMEM complete medium under the condition, and collecting 5 × 10 when growth state is good6Inoculating the cells into Balb/c mice subcutaneously until the subcutaneous tumor grows to 200 mm3Left and right for standby.
(2) Experimental grouping and nanoprobe dose selection: iron trioxide/gold nanocomposites (Fe) synthesized with 800 μ g/body of example 1 or example 22O3/Au) is modified by polyethylene glycol to obtain Fe2O3Au-PEG (specifically prepared by dissolving 10 mg of PEG in 2 mL of water and adding to 20 mL of solution containing 10 mg of Fe2O3In Au solution, and then continuously stirring for 24 h to obtain Fe2O3Au-PEG) of the iron-containing alloy, and mixing the Fe with the alloy2O3And the toxicity of Balb/c mice is detected by Au-PEG, and the mice normally move and do not die. The experimental injection of 400. mu.g/body of probe and injection volume of 100. mu.L was selected with reference to the relevant literature and the above results. Mice were then randomly grouped. A probe control group and a light control group are respectively set up.
(3) Combination therapy: the iron trioxide/gold nanocomposite (Fe) synthesized in example 1 or example 2 was injected into the tail vein2O3/Au) is modified by polyethylene glycol to obtain Fe2O3Au-PEG (specifically prepared by dissolving 10 mg of PEG in 2 mL of water and adding to 20 mL of solution containing 10 mg of Fe2O3In Au solution, and then continuously stirring for 24 h to obtain Fe2O3/Au-PEG），Fe2O3The dosage of Au-PEG is 400 mu g/Au, and the illumination is carried out after 12 h (808 nm, 1W/cm)2，10 min）。
(4) The body weight and the tumor volume of the mice are recorded every day, and the tumor volume of the experimental group is found to be greatly inhibited, and other groups have no obvious inhibition phenomenon. The probe can be used for the combined treatment of mouse subcutaneous tumors.
FIG. 6 shows that the synthesized nanoprobe of the present invention can well inhibit the growth of tumor in mice by the combined therapy of hunger/iron death/photothermal, and the other groups have little or poor inhibition effect.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A kind of utensilIron trioxide/gold nanocomposites (Fe) with cascaded catalytic action2O3The preparation method of the/Au-PEG) nano probe is characterized by comprising the following steps:
(1) synthesizing FeOOH by a hydrothermal method;
(2) SiO the FeOOH obtained in the step (1)2To obtain SiO2Encapsulated FeOOH @ SiO2;
(3) For FeOOH @ SiO obtained in the step (2)2High-temperature calcining is carried out to obtain alpha-Fe2O3；
(4) For alpha-Fe obtained in the step (3)2O3Modifying the gold nanoparticles to obtain Fe2O3/Au；
(5) For Fe obtained in the step (4)2O3/Au is modified by polyethylene glycol to obtain Fe2O3/Au-PEG。
2. The preparation method according to claim 1, wherein the step (1) is specifically prepared by: dissolving a certain amount of ferric chloride hexahydrate in water, transferring the solution into a round-bottom flask, and continuously stirring the solution at 80 ℃ under the condition of refluxing condensed water to obtain a hydrolysate FeOOH.
3. The preparation method according to claim 1, wherein the step (2) comprises the following specific steps: dissolving FeOOH in ethanol, adding CTAB, ammonia water and TEOS under continuous stirring, and stirring for a long time to obtain SiO2Encapsulated FeOOH @ SiO2。
4. The preparation method according to claim 1, wherein the step (3) comprises the following specific steps: FeOOH @ SiO2Dissolving in ethanol, and dropwise adding ammonia water for a few times; then calcining the reaction solution at high temperature to obtain Fe2O3@SiO2(ii) a Finally, the SiO is etched by adding NaOH2To obtain Fe2O3。
5. The preparation method according to claim 1, wherein the step (4) comprises the following specific steps: mixing Fe2O3Dissolving in ethanol, adding gold nanoparticles, and continuously stirring to obtain Fe2O3/Au。
6. The preparation method according to claim 1, wherein the step (5) comprises the following specific steps: mixing Fe2O3Dissolving Au in ethanol, adding polyethylene glycol, and continuously stirring to obtain Fe2O3/Au-PEG。
7. Iron trioxide/gold nanocomposites (Fe) with cascade catalysis obtained by the process of any one of claims 1 to 62O3/Au) nanoprobe.
8. The iron trioxide/gold nanocomposite (Fe) according to claim 72O3The application of the/Au) nano probe is characterized by being applied to the preparation of the nano probe for treating tumors.
9. The use of claim 8, wherein the tumor treatment nanoprobe is a starvation, iron death, photothermal tumor treatment nanoprobe.
10. Use according to claim 8, wherein the iron sesquioxide/gold nanocomposite (Fe) is applied before use2O3and/Au) nano probe is modified by polyethylene glycol.
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